Phenylhydrazone derivatives

ABSTRACT

1. A PHENYLHYDRAZONE DERIVATIVE OF THE FORMULA:   AR-NH-N=C(-CL)-R   WHEREIN R REPRESENTS ALKYL OF 1 THROUGH 10 CARBON ATOMS AND AR REPRESENTS PHENYL SUBSTITUTED BY THREE ATOMS OR RADICALS SELECTED FROM HALOGEN, ALKYL OF 1 THROUGH 4 CARBON ATOMS, ALKOXY OF 1 TO 4 CARBON ATOMS, ALKENYLOXY OF 2 THROUGH 4 CARBON ATOMS AND ALKYNYLOXY OF 2 THROUGH 4 CARBON ATOMS AT LEAST ONE OF THE SUBSTITUENTS ON THE PHENYL RADICAL BEING AN ALKOXY, ALKENYLOXY OR ALKYNYLOXY RADICAL.

United States Patent 3,839,445 PHENYLHYDRAZONE DERIVATIVES Roger Boesch,Vitry-sur-Seine, France, assignor to Rhone-Poulenc S.A., Paris, FranceNo Drawing. Filed May 24, 1973, Ser. No. 363,652 Claims priority,application France, May 26, 1972, 7218895; Mar. 19, 1973, 7309753 Int.Cl. C07c 109/14 US. Cl. 260-566 B 18 Claims ABSTRACT OF THE DISCLOSUREPhenylhydrazone derivatives of the formula:

wherein R represents alkyl of 1 to carbon atoms and Ar represents phenylsubstituted by three atoms or radicals selected from halogen, alkyl of 1to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkenyloxy of 2 to 4carbon atoms and alkynyloxy of 2 to 4 carbon atoms, at least one of thesubstituents on the phenyl radical being an alkoxy, alkenyloxy oralkynyloxy radical, which are new compounds, possess insecticidal andacaricidal properties.

This invention relates to new phenylhydrazone derivatives, to a processfor their preparation and to composi tions containing them.

The phenylhydrazone derivatives of the present invention are those ofthe general formula:

wherein R represents an alkyl radical containing 1 to 10 carbon atoms,and Ar represents a phenyl radical substituted by three atoms orradicals, which may be the same or different, selected from halogen(preferably chlorine) atoms, alkyl radicals containing 1 to 4 carbonatoms, alkoxy radicals containing 1 to 4 carbon atoms, alkenyloxyradicals containing 2 to 4 carbon atoms and allrynyloxy radicalscontaining 2 to 4 carbon atoms, at least one of the substituents on thephenyl radical being an alkoxy, alkenyloxy or alkynyloxy radical. It isto be understood that alkyl radicals represented by symbol R, and alkyl,alkoxy, alkenyloxy and alkynyloxy radicals present on the phenyl radicalAr may have straightor branched-carbon chains.

According to a feature of the invention, the phenylhydrazone derivativesof general formula I are prepared by the action of a chlorinating agent,such as phosphorus pentachloride, phosphorus oxychloride or thionylchloride, on a phenylhydrazide of the general formula:

Ar NHNHCO-R II wherein R and Ar are as hereinbefore defined.

Preferably phosphorus pentachloride is used as the chlorinating agentand the reaction can then be represented schematically in the followingmanner:

Patented Oct. 1, 1974 wherein the symbols R and Ar are as hereinbeforedefined, and Ar, represents a phenyl radical which is optionallysubstituted, for example by an alkyl radical.

Conversion of the grouping NH-COR in the phenylhydrazides of generalformula II into a grouping is generally effected by heating thephenylhydrazide of general formula II and phosphorous pentachloride inan inert organic solvent such as carbon tetrachloride or ethyl acetate,preferably at the reflux temperature of the solvent employed, e.g. aboutC. Decomposition of the phosphorylated complex obtained can be effectedby heating with a phenol in the same inert organic solvent.

When thionyl chloride is employed as the chlorinating agent the reactioncan be represented schematically as follows:

wherein R and Ar are as hereinbefore defined. Generally the reaction iseffected by heating the reactants in an inert organic solvent such ascarbon tetrachloride preferably at the reflux temperature of the solventemployed, e.g. about 80 C.

The phenylhydrazides of general formula II can be obtained by the actionof an acid of the general formula:

R-COOH III (wherein R is as hereinbefore defined), or a derivative ofthe acid, such as a halide or the anhydride, on a phenylhydrazine of thegeneral formula:

Ar-NH-NH IV wherein Ar is as hereinbefore defined. The reaction isgenerally carried out in an inert organic solvent such as methylenechloride, ethyl acetate or an aromatic hydrocarbon such as benzene.

The phenylhydrazines of general formula IV can be obtained bydiazotization of an aniline of the general formula:

Ar-NH V (wherein Ar is as hereinbefore defined) and reduction of theresulting diazonium salt.

The phenylhydrazone derivatives of general formula I obtained by theafore-described process can optionally be purified by application ofphysical methods such as crystallisation or chromatography.

The new compounds of general formula I possess particularly interestinginsecticidal and acaricidal properties. The insecticidal activity ismanifest more particularly by contact against diptera (MusCa domestica),coleoptera (Tribolium confusum) and lepidoptera (Plutella maculipenniscaterpillars) at doses between 10 and g. of active material perhectolitre of liquid diluent. The acaricidal activity is interestingagainst phytophagous acarids (Tetranychus telarius) at doses between 1and 100 g. of active material per hectolitre of liquid diluent. At dosesbetween 1 and 200 g. of active material per hectolitre of liquiddiluent, the phenylhydrazone derivatives of general formula I show aconsiderable ovidical activity.

Of particular interest are those phenylhydrazone derivatives of generalformula I in which the three substituents on the phenyl nucleus are inpositions 2-, 4- and and which can be represented by the generalformula:

R3 VI wherein R represents an alkyl radical containing 1 to 4 carbonatoms, R represents a halogen atom or an alkoxy radical containing 1 to4 carbon atoms, or an alkenyloxy or alkynyloxy radical containing 2 to 4carbon atoms, R represents a halogen atom, or an alkyl or alkoxy radicalcontaining 1 to 4 carbon atoms, or an alkenyloxy or alkynyloxy radicalcontaining 2 to 4 carbon atoms, one of the symbols R and R representingan alkoxy, alkenyloxy or alkynyloxy radical, and R represents a halogenatom, preferably chlorine. When one of the symbols R and R represents ahalogen atom, the atom is preferably chlorine.

Compounds of general formula VI of outstanding importance are those inwhich R' represents the methyl, ethyl, propyl, isopropyl, isobutyl ort.-butyl radical, R represents an isopropoxy, allyloxy or propargyloxyradical, and R and R represent chlorine atoms, for example 1-2,4-dichloro-S-propargyloxyphenyl-hydrazono) -1- chloro-Z-methylpropane,

1-(2,4-dichloro-5-propargyloxyphenyl-hydrazono)-1-chloro-2,Z-dimethylpropane,

1- 2,4-dichloro-S-propargyloxyphenyl-hydrazono) 1- chloroethane,

l-( 2,4-dichloro-S-isopropoxyphenyl-hydrazono) -1- chloro-2-methylpropane,

1- (2,4-dichloro-5-propargyloxyphenyl-hydrazono) -1- chloropropane,

1-(2,4-dichloro-S-propargyloxyphenyl-hydrazono)-1-chloro-3-methylbutane,

l- 2,4-dichloro-5-isopropoxyphenyl-hydrazono)-1- chlorobutane,

1- 2,4-dichloro-S-isopropoxyphenyl-hydrazono) -1-chloro- 3-methylbutane,

1- (2,4-dichloro-5-propargyloxyphenyl-hydrazono) -1- chlorobutane,

l-(2,4-dichloro-S-isopropoxyphenyl-hydrazono)-1-chloro-2,2-dimethylpropane,

1- 2,4-dichloro-S-allyloxyphenyl-hydrazono) l-chloro- 2,2-dimethylpropane,

l- 2,4-dichloro-5-allyloxyphenyl-hydrazono) -1-chloroethane and 1-(2,4-dichloro-5-isopropoxyphenyl-hydrazono) lchlo ropro pane,

especially the first-mentioned compound.

According to a further feature of the present invention, there areprovided insecticidal and acaricidal compositions which contain, as theactive ingredient, at least one of the phenylhydrazone derivatives ofgeneral formula I in association with one or more diluents or adjuvantscompatible with the phenylhydrazone derivative(s) and suitable for usein agriculture.

These compositions can optionally contain other compatible pesticidessuch as fungicides (e.g. maneb). Preferably the compositions containbetween 0.005% and 80% by weight of phenylhydrazone derivative.

The compositions may be solid if there is employed a powdered solidcompatible diluent such as talc, calcined magnesia, kieselguhr,tricalcium phosphate, powdered cork, adsorbent charcoal, or a clay suchas kaolin or bentonite. These solid compositions are preferably preparedby grinding the phenylhydrazone derivative with the solid diluent, or byimpregnating the solid diluent with a solution of the phenylhydrazonederivative in a volatile solvent, evaporating the solvent, and ifnecessary grinding the product so as to obtain a powder.

Instead of a solid diluent, there may be used a liquid in which thephenylhydrazone derivative is dissolved or dispersed. The compositionsmay thus take the form of suspensions, emulsions or solutions in organicor aqueousorganic media, for example aromatic hydrocarbons such astoluene or xylene, mineral, animal or vegetable oils, or acetophenone,or mixtures of these diluents. The compositions in the form ofsuspensions, emulsions or solutions may contain wetting, dispersing oremulsifying agents of the ionic or non-ionic type, for examplesulphoricinoleates, quaternary ammonium derivatives or products based oncondensates of ethylene oxide such as the condensates of ethylene oxidewith octylphenol, or fatty acid esters of anhydrosorbitols which havebeen rendered soluble by etherification of the free hydroxyl groups bycondensation with ethylene oxides. It is preferable to use agents of thenon-ionic type because they are not sensitive to electrolytes. Whenemulsions are required the phenylhydrazone derivatives may be used inthe form of self-emulsifying concentrates containing the activesubstance dissolved in the emulsifying agent or in a solvent containingan emulsifying agent compatible with the phenylhydrazone derivative andsolvent, a simple addition of Water to such concentrates producingcompositions ready for use.

The phenylhydrazone derivatives of general formula I are preferablyemployed for insecticidal and acaricidal purposes in quantities of 10 tog. per hectolitre of water, but lower concentrations can also be usedeffectively.

The following Example illustrates the preparation of phenylhydrazonederivatives of general formula I.

EXAMPLE 1 A suspension of 1 isobutyryl 2 (2,4-dichloro-5-propargyloxyphenyl)hydrazine (30.1 g.) and phosphorus pentachloride(21.5 g.) in carbon tetrachloride (200 cc.) is heated under reflux untilthe evolution of gas ceases. To the solution obtained there is added,after cooling to 20 C., phenol (32.4 g.) dissolved in carbontetrachloride cc.) and the mixture is then heated until the evolution ofgas ceases whilst taking the reaction mixture progressively to thereflux temperature. The solvent is evaporated under reduced pressure (20mm, Hg) at 50 C. and the residual solid is stirred with di-isopropylether (100 cc.). The crystals which are formed are filtered off, washedwith di-isopropyl ether cooled to 5 C. (2X 10 cc.) and dried underreduced pressure (0.5 mm. Hg) at 20 C. to yield1-(2,4-dichloro-5-propargyloxyphenyl-hydrazono)-1-chloro-2-methylpropane(23 g.) melting at 103 C.

1 Isobutyryl 2 (2,4 dichloro-S-propargyloxyphenyl)-hydrazine (m.p. 162and then 169 C.), which is employed as starting material, can beobtained by the action of isobutyryl chloride on2,4-dichloro-5-propargyloxyphenyl-hydrazine in ethyl acetate in thepresence of triethylamine.

2,4-Dichloro 5 propargyloxyphenyl hydrazine, m.p. 132 C., can beobtained by the action of sodium nitrite on2,4-dichloro-S-propargyloxy-aniline in hydrochloric acid (d=1.18)followed by reduction of the diazonium salt thus formed with stannouschloride.

2,4 Dichloro-S-propargyloxy-aniline, m.p. 90 C., can be prepared by thereduction of the corresponding nitro derivative by means of iron inaqueous ethanol.

2,4 Dichloro-5-propargyloxy-nitrobenzene, m.p. 66 C., can be prepared bythe action of propargyl chloride on 2,4-dichloro-S-nitrophenol inacetonitrile under reflux in the presence of potassium carbonate.

By proceeding as described in the foregoing Example and starting withappropriate phenylhydrazides of general formula II, there can beprepared the following phenylhydrazone derivatives conforming to generalformula I:

1-(2,4-dich1oro-5-propargyloxyphenyl-hydrazono)-1-chloro-2,2-dimethylpropane, m.p. 67, then 77 C.;

1-(2,4-dichloro-5-propargyloxyphenyl-hydrazono)-1- chloroethane, mp. 143C.;

1- (2,4-dichloro-5-isopropoxyphenyl-hydrazono -1-chloro-Z-methylpropane, solidification point 38 C.;

1-(2,4-dichloro-S-propargyloxyphenyl-hydrazono)-1- chloropropane, mp.100 C.;

1-(2,4-dichloro-S-propargyloxyphenyl-hydrazono)-1-chloro-3-methylbutane, an oil;

1-(2,4-dichloro-5-isopropoXyphenyl-hydrazono)-1-chlorobutane, an oil;

1-(2,4-dichloro-S-isopropoxyphenyl-hydrazono) -1-chloroheptane, an oil;

1- (2,4-dichloro-S-isopropoxyphenyl-hydrazono )-1-chlorooctane, an oil;

1- (2,4-dichloro-5-isopropoxyphenyl-hydrazono -1-chloro- 3-methylbutane,an oil;

1-(2,4-dichloro-5-propargyloXyphenyl-hydrazono)-1- chlorobutane, an oil;

1-(2,4-dichloro-5-isopropoxyphenyl-hydrazono)-1-chloro-2,2-dimethylpropane, solidification point 34 C.;

1-(2,4-dichloro-S-methoxyphenyl-hydrazono)-1-chloropropane, rn.p. 7071C.;

1- (2,4-dichloro-5-methoxyphenyl-hydrazono) -1-chlor0-2,2-dimethylpropane, mp. 118-119 C.;

1- (2,4-dichloro-5 -al1yloxyphenyl-hydrazono l-chloro-2,2-dimethylpropane, m.p. 87 C.;

1-(2,4-dichloro-5-methoXyphenyl-hydrazono)-1-chlorobutane, m.p. 70 C.;

1'- (2,4-dichloro-5-allyloxyphenyl-hydrazono -1-chloro ethane, m.p. 87C.;

1-(2,4-dichloro-5-isopropoxypheny1-hydrazono)-1-ch1oropropane,solidification point 27 C.;

1-(2,4-dichloro-5-sec-butoxyphenyl-hydrazono)-1-chloroethane, m.p. 47C.;

1-(2,4-dich1oro-5-sec-butoxyphenyl-hydrazono)-1-chloropropane,solidification point 27 C.;

1- (2,4-dichloro-S-sec-butoxyphenyl-hydrazono) -1-chlorobutane,solidification point 29 C.; e

1- (2,4-dichloro-5-sec-butoxyphenyl-hydrazono) -1-chloro- 2methypropane,an oil;

1-(2,4-dichloro-S-ethoxyphenyl-hydrazono)-1-chloropropane, mp. 64, then67 C.;

1-(2,4-dichloro-S-ethOxyphenyl-hydrazono)-1-chlorobutane, m.p. 77 C.;

1- (2,4-dichloro-5-ethoxyphenyl-hydrazono) -1-chloro-2- methylpropane,m.p. 68 C.;

1- (2,4-dichloro-5-ethoxyphenyl-hydrazono) -1-chloro-2,2-

dimethylpropane, mp. 121 C.;

1-(2,5-dichloro-4-propargyloxyphenyl-hydrazono)-1-chloro-2,2-dimethylpropane, mp. 71 C.;

1- 2-chloro-4-Inethyl-5-propargyloxyphenyl-hydrazono 1-chlorobutane,m.p. 57 C.;

1-(2,5-dichloro-4-propargyloxyphenyl-hydrazono)-1-chloro-2-methylpropane, rn.p. 94 C.;

1- 2-chloro-4-methyl-5-prop argyloXyphenyl-hydrazono l-chloropropane,m.p. 74 C.;

1-(2-chloro-4-methyl-S-propargyloxyphenyl-hydrazono)- l-chloroethane,m.p. 90 C.;

1- (2,S-dichloro-4-propargyloxyphenyl-hydrazono -1- chloroethane, mp.103 C.;

1- (2, 5-dichloro-4-propargyloXyphenyl-hydrazono) -1- chloropropane,m.p. 87 C., and

1-(2,S-dichloro-4-propargyloxyphenyl-hydrazono)-1- chlorobutane,solidification point 38 C.

The products obtained as oils are characterised by elementary analysisand infra-red spectra.

EXAMPLE 2 molecule of octylphenol are added to 20 g. of 1-(2,4-dichloro5 propargyloXyphenyl-hydrazono)-1-chloro-2- methylpropane, and a mixtureof equal volumes of toluene and acetophenone are added until the mixturereaches 100 cc.

The solution thus obtained is used after suitable dilution with water todestroy acarids.

According to the effect required concentrations of 1 to 100 g. ofphenylhydrazone derivative per hectolitre of water give good results.

EXAMPLE 3 To 50 parts of 1-(2,4-dichloro-5-propargyloxyphenylhydrazono)1 chloro-Z-methylpropane there are added 1 part of Tween (themono-oleate of a polyoxyethylene derivative of sorbitol), 20 parts ofcalcium lignosulphite and 29 parts of kieselguhr. After grinding andsieving, the powder obtained is utilised after dilution with water todestroy acarids.

The parts referred to above are parts by weight.

I claim:

1. A phenylhydrazone derivative of the formula:

wherein R represents alkyl of 1 through 10 carbon atoms and Arrepresents phenyl substituted by three atoms or radicals selected fromhalogen, alkyl of 1 through 4 carbon atoms, alkoxy of 1 through 4 carbonatoms, alkenyloxy of 2 through 4 carbon atoms and alkynyloxy of 2through 4 carbon atoms, at least one of the substituents on the phenylradical being an alkoxy, alkenyloxy or alkynyloxy radical.

2. A phenylhydrazone derivative according to claim 1 'wherein anyhalogen substituent on the phenyl radical is chlorine.

3. A phenylhydrazone derivative according to claim 1 of the formula:

wherein R represents alkyl of 1 through 4 carbon atoms, R representshalogen, or alkoxy of 1 through 4 carbon atoms, or alkenyloxy oralkynyloxy of 2 through 4 carbon atoms, R represents halogen, or alkylor alkoxy of 1 through 4 carbon atoms, or alkenyloxy or alkynyloxy of 2through 4 carbon atoms, one of the symbols R and R representing analkoxy, alkenyloxy or alkynyloxy radical, and R represents halogen.

4. A phenylhydrazone derivative according to claim 3 wherein one of thesymbols R and R represents chlorine and the other represents an alkoxy,alkenyloxy or alkynyloxy radical, and R represents chlorine.

5. A phenylhydrazone derivative according to claim 3 in which Rrepresents methyl, ethyl, propyl, isopropyl, isobutyl or t.-butyl, Rrepresents isopropoxy, allyloxy or propargyloxy, and R and R representchlorine.

6. The phenylhydrazone derivative according to claim 1 which is 1(2,4-dichloro-5-propargyloxyphenylhydrazono)-1-chloro-2-methylpropane.

7. The phenylhydrazone derivative according to claim 1 which is 1(2,4-dichloro-5-propargyloxyphenylhydrazono)-1-chloro-2,Z-dimethylpropane.

8. The phenylhydrazone derivative according to claim 1 which is 1(2,4-dichloro-5-propargyloxyphenylhydrazono -1-chloroethane.

9. The phenylhydrazone derivative according to claim 1 which is 1(2,4-dichloro-S-isopropoxyphenylhydrazono)-1-chloro-2-methylpropane.

10. The phenylhydrazone derivative according to claim 1 which is 1(2,4-dichloro-5-propargyloxyphenylhydrazono)-1-chloropropane.

11. The phenylhydrazone derivative according to claim 1 which is 1(2,4-dichloro-5-propargyloxyphenylhydra- 2on0)-l-chloro-3-methylbutane.

12. The phenylhydrazone derivative according to claim 1 which is 1 (2,4dichl0ro-5-isopropoxyphenylhydrazono)-1-chlorobutane.

13. The phenylhydrazone derivative according to claim 1 which is 1 (2,4dichloro-5-isopropoxyphenylhydrazon0)-l-chloro-3-methylbutane.

14. The phenylhydrazone derivative according to claim 1 which is 1(2,4-dichlor0-5-pr0pargyloxyphenylhydra- Z0n0)-1-chlor0butane.

15. The phenylhydrazone derivative according to claim 1 which 1(2,4-dichloro-5-is0propoxyphenylhydrazono)-1-chloro-2,2-dimethylpropane.

16. The phenylhydrazone derivative according to claim 1 which is l(2,4-dichloro-S-allyloxyphenylhydrazono)- 1-chloro-2,Z-dimethylpropane.

17. The phenylhydrazonc derivative according to claim 1 which is 1(2,4-dichloro-5-allyloxyphenylhydrazono)- l-chloroethane.

References Cited UNITED STATES PATENTS 1/1972 Druber et al. 260-566 BOTHER REFERENCES Chemical Abstr., vol. 49, column 13140(d).

BERNARD HELFIN, Primary Examiner G. A. SCHWARTZ, Assistant Examiner US.Cl. X.R.

1. A PHENYLHYDRAZONE DERIVATIVE OF THE FORMULA: